Method, system, and device for storage and delivery of process gas from a substrate

ABSTRACT

Provided herein are methods, systems, and devices incorporating use of materials to store, ship, and deliver process gases to micro-electronics fabrication processes and other critical process applications.

CROSS REFERENCE TO RELATED APPLICATION(S)

This application is a continuation of U.S. Ser. No. 16/764,308, filedMay 14, 2020, now pending, which is a US national phase applicationunder 35 U.S.C. § 371 of international patent application no.PCT/US2018/061478, filed Nov. 16, 2018, which claims the benefit ofpriority under 35 U.S.C. § 119(e) of U.S. Ser. No. 62/587,759, filedNov. 17, 2017, of U.S. Ser. No. 62/651,589, filed Apr. 2, 2018, and ofU.S. Ser. No. 62/665,168, filed May 1, 2018. The entire content of eachof which is incorporated herein by reference.

BACKGROUND OF THE INVENTION Field of the Invention

The invention relates generally to process gases, and more specifically,to the use of materials to store, ship, and deliver process gases tomicro-electronics fabrication and other critical process applications.

Background Information

Various process gases may be used in the manufacturing and processing ofmicro-electronics. In addition, a variety of chemicals may be used inother environments demanding high purity gases, e.g., critical processesor applications, including without limitation microelectronicsapplications, wafer cleaning, wafer bonding, photoresist stripping,silicon oxidation, surface passivation, surface nitridation,photolithography mask cleaning, atomic layer deposition, chemical vapordeposition, flat panel displays, disinfection of surfaces contaminatedwith bacteria, viruses, DNA, and other biological agents, industrialparts cleaning, pharmaceutical manufacturing, production ofnano-materials, power generation and control devices, fuel cells, powertransmission devices, and other applications in which process controland purity are critical considerations. In those processes andapplications, it is necessary to deliver specific amounts of certainprocess gases under controlled operating conditions, e.g., temperature,pressure, and flow rate.

For a variety of reasons, gas phase delivery of process chemicals ispreferred to liquid phase delivery. For applications requiring low massflow for process chemicals, liquid delivery of process chemicals is notaccurate or clean enough. Gaseous delivery would be desired from astandpoint of ease of delivery, accuracy, and purity. Gas flow devicesare better attuned to precise control than liquid delivery devices.Additionally, micro-electronics applications and other criticalprocesses typically have extensive gas handling systems that makegaseous delivery considerably easier than liquid delivery. One approachis to vaporize the process chemical component directly at or near thepoint of use. Vaporizing liquids provides a process that leaves heavycontaminants behind, thus purifying the process chemical. However, forsafety, handling, stability, and/or purity reasons, many process gasesare not amenable to direct vaporization.

Ozone is a gas that is typically used to clean the surface ofsemiconductors (e.g., photoresist stripping) and as an oxidizing agent(e.g., forming oxide or hydroxide layers). More recently, hydrogenperoxide has been explored as a replacement for ozone in certainapplications. However, hydrogen peroxide has been of limited utilitybecause highly concentrated hydrogen peroxide solutions present serioussafety and handling concerns and obtaining high concentrations ofhydrogen peroxide in the gas phase has not been possible using existingtechnology. Hydrogen peroxide is typically available as an aqueoussolution. In addition, because hydrogen peroxide has a relatively lowvapor pressure (boiling point is approximately 150° C.), availablemethods and devices for delivering hydrogen peroxide generally do notprovide hydrogen peroxide containing gas streams with a sufficientconcentration of hydrogen peroxide.

Hydrazine has been widely used as rocket fuel, and its properties ofbeing highly explosive, highly reactive, and highly toxic are well known(Eckart Walter Schmidt, Hydrazine and Its Derivatives: Preparation,Properties, Applications, 2nd Edition, Wiley-Interscience, 2001). Earlystudies have shown the potential viability of Hydrazine (N₂H₄) and itsderivatives as a low temperature nitrogen source in chemistry vapordeposition (CVD) and atomic layer deposition (ALD). Thus, hydrazinepresents an opportunity to explore lower temperatures in part because ofthe favorable thermodynamics of hydrazine resulting in lower depositiontemperatures and a spontaneous reaction to form nitrides. Althoughreported in the literature (Burton et al. J. Electrochem. Soc., 155(7)0508-0516 (2008)), hydrazine usage has not been adopted commercially dueto significant safety concerns with using hydrazine.

As explained in International Publication Nos. WO2016/065132 andWO2017/181013, and PCT App. No. PCT/US2018/022686 by Rasirc, Inc., whichare incorporated by reference herein, the gas phase use of processchemicals has been limited by safety, handling, and purity concerns.Since the gas phase of many of such process chemicals have low flashpoints and can be explosive, semiconductor industry protocols for safehandling of these materials are very limited. Thus, a need exists forthe safe packing, shipping, storing, and usage of process gases.

SUMMARY OF THE INVENTION

The invention relates generally to process gases and more specificallyto the use of materials, such as porous materials, to store, ship, anddeliver process gases to micro-electronics fabrication and othercritical process applications. Accordingly, in one aspect, the inventionprovides a solid storage device for a process solution. The storagedevice includes a housing with a substrate disposed therein; a processsolution contained within the housing and in fluid contact with thesubstrate such that the solution is adsorbed onto the substrate, therebydiluting the solution within the substrate; and a head space containedwithin the housing and separated from the process solution by thesubstrate. In various embodiments, the housing is configured to allow acarrier gas to flow through the head space or is configured to allow avacuum to be drawn through the head space to produce a gas streamcomprising a gas phase of the process solution to deliver the gas streamto a critical process, application or storage vessel. In certainembodiments, the quantity of the process solution in the device is about30 to 1900 weight percent of the process solution/substrate complex. Incertain embodiments, the quantity of the process solution in the deviceis about 30 to 800 weight percent of the process solution/substratecomplex. In certain embodiments, the quantity of the process solution inthe device is about 30 to 100 weight percent of the processsolution/substrate complex.

In various embodiments, the process solution is selected from a groupconsisting of hydrogen peroxide, hydrazine, mono-methyl hydrazine,tertiary butyl hydrazine, dimethylhydrazine, and any derivative thereof.In various embodiments, the process solution is a liquid solution or agaseous solution, such as an aqueous hydrogen peroxide solution, ananhydrous hydrogen peroxide solution, an aqueous hydrazine solution, oran anhydrous hydrazine solution. In various embodiments, the anhydroushydrogen peroxide solution or anhydrous hydrazine solution contains lessthan 2%, 0.5%, 0.1%, 0.01%, 0.001%, 0.0001% or 0.00001% water.

In various embodiments, the substrate is a porous structure with asurface area ranging from 100 to 1000 m²/g. In various embodiments, thevarious is configured to adsorb over 42% w/w hydrogen peroxide. Invarious embodiments, the substrate is configured to adsorb over 50% w/whydrogen peroxide. In various embodiments, the concentration of thehydrogen peroxide solution is over 100% w/w. In various embodiments, theconcentration of the hydrogen peroxide solution is over 200% w/w. Invarious embodiments, the concentration of hydrogen peroxide is over 800%w/w. In various embodiments, the concentration of hydrogen peroxide isover 1000% w/w. In various embodiments, the concentration of hydrogenperoxide is over 1900% w/w. In various embodiments, the concentration ofthe hydrogen peroxide solution is below 30% w/w. In various embodiments,the concentration of the hydrogen peroxide solution is stable over acourse of a known period of time, such as no less than approximately 100hours.

In certain embodiments, wherein the substrate is formed as a fabric, apowder, one or more bricks, one or more blocks, one or more beads, oneor more particles, one or more extrudates, or one or more pellets. Incertain embodiments, the substrate is a non-woven fabric that has beentreated with a mechanical finishing process selected from the groupconsisting of spun bonding, needle bonding, perforation bonding,carding, and any combination thereof. In certain embodiments, thenon-woven fabric is a PTFE fabric. In certain embodiments, the substrateis formed as a mesh.

In certain embodiments, the substrate is formed from a material selectedfrom the group consisting of alumina, aluminum oxide, titanium dioxide,silica, silicon dioxide, quartz, activated carbon, carbon molecularsieve, carbon pyrolyzate, polytetrafluoroethylene (PTFE), polyester(PE), polyethylene terephthalate (PET), polyethylene/polyethyleneterephthalate co-polymer, polypropylene (PP), rayon, zirconium oxide,zeolite, high silica zeolite, polymethylpentene (PMP), polybutyleneterephthalate (PBT), polyethylene/polypropylene co-polymers, HydrophilicHigh Density Polyethylene (HDPE), Hydrophobic High Density Polyethylene(HDPE), Hydrophilic UHMW Polyethylene, Hydrophobic UHMW Polyethlyene,perfluoroalkoxy alkane (PFA), polyvinylidene fluoride (PVF), silk,tencel, sponge materials, polyethylene glycol (PEG), polyvinyl alcohol(PVA), and/or polyvinylpyrrolidone (PVP), polypyridine, polyacrylates,polyacrylic acid, polyacrylic acid/acrylate co-polymers, polycarbonates,polyacrylamides, polyacrylate/acrylamide co-polymers, cellulosicmaterials, and any combination thereof. In various embodiments, the meshsubstrate is spiral-wound within the housing.

In various embodiments, the storage device includes a separator disposedadjacent to the mesh, wherein the separator is configured to support andseparate layers of the spiral-wound mesh. In certain embodiments, theseparator is formed from PTFE.

In various embodiments, the substrate is a hydrogel selected from thegroup consisting of polyethylene glycol (PEG), polyvinyl alcohol (PVA),polyvinylpyrrolidone (PVP), polypyridine, and any combination thereof.In various embodiments, the hydrogel is a 20% PEG hydrogel or a 40% PEGhydrogel. In certain embodiments, the hydrogel is wrapped in a PTFE meshand/or may further include a separator disposed adjacent to the mesh.

In another aspect, the invention provides a method for delivering a gas.The method includes contacting a process solution with a substratewithin an enclosed housing such that the solution is adsorbed onto thesubstrate, thereby diluting the process solution within the substrate;exposing the substrate to a carrier gas or a vacuum, thereby forming agas stream comprising a gas phase of the process solution; anddelivering the gas stream to a critical process, application, or storagevessel. The housing may be configured to allow the carrier gas to flowthrough a head space contained within the housing or is configured toallow vacuum to be drawn through the head space, and the head space maybe separated from the process solution by the substrate.

In another aspect, the invention provides a chemical delivery system.The system may include a process solution provided within a housing,wherein the process solution is in contact with a substrate disposedwithin the housing such that the solution is adsorbed onto thesubstrate, thereby diluting the process solution within the substrate.The chemical delivery system may also include a carrier gas or vacuum influid contact with the gas phase in the head space of the processsolution, thereby forming a transportable gas stream within the headspace. The chemical delivery system may further include an apparatus influid communication with the housing and used for delivering the gasstream to a critical process, application or storage vessel. In variousembodiments, the housing allows the carrier gas to flow through a headspace contained within the housing or allows vacuum to be drawn throughthe head space.

The methods and systems provided herein may further comprise use ofvarious components for containing and controlling the flow of the gasesand liquids used therein. For example, the methods and systems mayinclude one or more mass flow controllers, valves, check valves,filters, pressure gauges, gas sensors, regulators, rotameters, andpumps. The methods and systems provided herein may also include variousheaters, thermocouples, and temperature controllers to control thetemperature of various components of the systems and steps of themethods.

Additional objects and advantages of the invention will be set forth inpart in the description which follows, and in part will be obvious fromthe description, or maybe learned by practice of the invention. Theobjects and advantages of the invention will be realized and attained bymeans of the elements and combinations particularly pointed out in theembodiments and claims.

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory onlyand are not restrictive of the invention.

The accompanying drawings, which are incorporated in and constitute apart of this specification, illustrate several embodiments of theinvention and, together with the description, serve to explain theprinciples of the invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a pictorial diagram showing a perspective cross-sectional viewof an exemplary embodiment of a storage device according to the presentinvention.

FIG. 2 is a pictorial diagram showing a perspective view of aspiral-wound substrate of the storage device according to variousembodiments of the present invention.

FIG. 3 is a pictorial diagram showing a perspective view of an exemplaryembodiment of a storage device according to the present invention.

FIGS. 4A and 4B are pictorial diagrams showing an exemplary storagedevice containing a wick substrate according to various embodiments ofthe present invention.

FIG. 4C is a pictorial diagram showing a cross-sectional view of astorage device containing a hydrogel substrate according to variousembodiments of the present invention.

FIG. 4D is a pictorial diagram showing a cross-sectional view of astorage device containing a hydrogel substrate taken along line D-D ofFIG. 14C according to various embodiments of the present invention.

FIG. 4E is a pictorial diagram showing a perspective view of a storagedevice according to various embodiments of the present invention.

FIG. 5 is a pictorial diagram of a P&ID used for testing according tovarious embodiments of the present disclosure.

FIG. 6 is a pictorial diagram of a P&ID used for testing according tovarious embodiments of the present disclosure.

FIGS. 7-18 are graphical diagrams showing vapor concentration outputs ofvarious substrates contained in a storage device according to variousembodiments of the present invention.

FIG. 19 is a graphical diagram showing vapor pressure rise overtemperature during the vapor pressure tests according to certainembodiments of the present disclosure.

FIG. 20 is a graphical diagram showing the results of vapor output usingnon-woven wick substrates contained in a storage device according tovarious embodiments of the present invention.

FIGS. 21-23 are graphical diagrams showing hydrogen peroxide vaporoutput using hydrogel substrates contained in a storage device accordingto certain embodiments of the disclosure.

Embodiments of the present disclosure and their advantages are bestunderstood by referring to the detailed description that follows. Itshould be appreciated that like reference numerals are used to identifylike elements illustrates in one or more of the figures.

DETAILED DESCRIPTION OF THE INVENTION

New generation semiconductor materials and architectures require newprecursors and oxidants for atomic layer deposition (ALD), atomic layeretch (ALE), and chemical vapor deposition (CVD) processes. Many liquidprocess chemical solutions used in these processes have the possibilityof leakage when a typical storage container containing the solutionruptures or other system components fail under pressure, impact, orheat. For example, hydrazine leaked into the environment can present anexplosion, fire, or physical hazard to those exposed. The presentinvention is therefore based on the observation that materials, such as,for example, porous materials, may be used to store, ship, and deliverprocess gases for micro-electronics fabrication and other criticalprocess applications while obviating the hazards posed by typicalstorage containers.

Before the present compositions and methods are described, it is to beunderstood that this invention is not limited to particularcompositions, configurations, methods, and experimental conditionsdescribed, as such compositions, configurations, methods, and conditionsmay vary. It is also to be understood that the terminology used hereinis for purposes of describing particular embodiments only, and is notintended to be limiting, since the scope of the present invention willbe limited only in the appended claims.

As used in this specification and the appended claims, the singularforms “a”, “an”, and “the” include plural references unless the contextclearly dictates otherwise. Thus, for example, references to “themethod” includes one or more methods, and/or steps of the type describedherein which will become apparent to those persons skilled in the artupon reading this disclosure and so forth.

The term “comprising,” which is used interchangeably with “including,”“containing,” or “characterized by,” is inclusive or open-ended languageand does not exclude additional, unrecited elements or method steps. Thephrase “consisting of” excludes any element, step, or ingredient notspecified in the claim. The phrase “consisting essentially of” limitsthe scope of a claim to the specified materials or steps and those thatdo not materially affect the basic and novel characteristics of theclaimed invention. The present disclosure contemplates embodiments ofthe invention compositions and methods corresponding to the scope ofeach of these phrases. Thus, a device, composition or method comprisingrecited elements or steps contemplates particular embodiments in whichthe composition or method consists essentially of or consists of thoseelements or steps.

“About” as used herein means that a number referred to as “about”comprises the recited number plus or minus 1-10% of that recited number.For example, “about” 100 degrees can mean 95-105 degrees or as few as99-101 degrees depending on the context. Whenever it appears herein, anumerical range such as “1 to 20” refers to each integer in the givenrange; i.e., meaning only 1, only 2, only 3, etc., up to and includingonly 20.

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Although any methods andmaterials similar or equivalent to those described herein can be used inthe practice or testing of the invention, the preferred methods andmaterials are now described.

The term “process gas” as used herein is a broad term, and is to begiven its ordinary and customary meaning to a person of ordinary skillin the art (and is not to be limited to a special or customizedmeaning), and refers without limitation to a gas that is used in anapplication or process, e.g., a step in the manufacturing or processingof micro-electronics and in other critical processes. Exemplary processgases are reducing agents, oxidizing agents, inorganic acids, organicacids, inorganic bases, organic bases, and inorganic and organicsolvents. Specific examples of process gases include, but are notlimited to, hydrazine and hydrogen peroxide.

The term “reactive process gas” as used herein is a broad term, and isto be given its ordinary and customary meaning to a person of ordinaryskill in the art (and is not to be limited to a special or customizedmeaning), and refers without limitation to a process gas that chemicallyreacts in the particular application or process in which the gas isemployed, e.g., by reacting with a surface, a liquid process chemical,or another process gas.

The term “non-reactive process gas” as used herein is a broad term, andis to be given its ordinary and customary meaning to a person ofordinary skill in the art (and is not to be limited to a special orcustomized meaning), and refers without limitation to a process gas thatdoes not chemically react in the particular application or process inwhich the gas is employed, but the properties of the “non-reactiveprocess gas” provide it with utility in the particular application orprocess.

The term “carrier gas” as used herein is a broad term, and is to begiven its ordinary and customary meaning to a person of ordinary skillin the art (and is not to be limited to a special or customizedmeaning), and refers without limitation to a gas that is used to carryanother gas through a process train, which is typically a train ofpiping. Exemplary carrier gases are nitrogen, argon, hydrogen, oxygen,CO2, clean dry air, helium, ammonia, or other gases that are stable atroom temperature and atmospheric pressure. In various embodiments, thecarrier gas may be a substantially dry carrier gas.

The term “head space” as used herein is a broad term, and is to be givenits ordinary and customary meaning to a person of ordinary skill in theart (and is not to be limited to a special or customized meaning), andrefers without limitation to a volume of gas in fluid contact with aprocess chemical solution (e.g., hydrazine) that provides at least aportion of the vapor phase (i.e., process gas) contained in the headspace. There may be a permeable or selectively permeable barrier whollyor partially separating the head space that is optionally in directcontact with the process chemical solution. In those embodiments wherethe membrane is not in direct contact with the process chemicalsolution, more than one head space may exist, i.e., a first head spacedirectly above the solution that contains the vapor phase of thesolution and a second head space separated from the first head space bya membrane that only contains the components of the first head spacethat can permeate the membrane, e.g., hydrazine. In those embodimentswith a hydrazine solution and a head space separated by a substantiallygas-impermeable membrane, the head space may be located above, below, oron any side of the chemical solution, or the head space may surround orbe surrounded by the hydrazine solution. For example, the head space maybe the space inside a substantially gas-impermeable tube running throughthe hydrazine solution or the hydrazine solution may be located inside asubstantially gas-impermeable tube with the head space surrounding theoutside of the tube. The head space is also the space surrounding thesubstrate in which the chemical solution is present in the gas phase ina manner that allows for transport to critical processes by way ofcarrier gas or vacuum.

As provided herein, the storage device of the present invention may beimplemented to act as a storage, shipping, and dispensing mechanism forprocess gases and solutions that may be dispensed as a controlled,high-purity vapor for use in various applications, such asmicro-electronics applications. In various embodiments, the substratemay have inert chemistry properties, porous structures with largesurface areas and high surface to volume ratios, and solid or semi-solidmorphology. As such, the substrate significantly improves the safety ofprocess gases, such as anhydrous hydrazine or hydrogen peroxide, duringpacking, shipping, storing, and using, and produce a high and stableoutput of the process gas vapor with a high purity.

Compared to known storage vessels used for anhydrous hydrazine gas andliquid hydrazine solutions containing other solvents, the presentinvention provides a storage device incorporating a substrate configuredto adsorb the process chemical solution, thereby providing the followingadvantages: (1) by turning the morphology of, e.g., hydrazine fromliquid into “solid,” the complex minimizes the dangerous level ofleakage should the storage device rupture and/or other system componentsfail (for example, failure of valves, joints, etc.); (2) the inertabsorbent/adsorbent materials used to form the substrate have goodcompatibility with anhydrous hydrazine such that no volatile or smallmolecules are produced during the storage and usage thereof (this alsoimproves safety while minimizing the amount of contaminants in thehydrazine vapor phase); (3) by not using a liquid solvent, the output ofanhydrous hydrazine from the storage device is not affected by othervolatile components in the vessel due to changes in concentration of thehydrazine, which follows Raoult's law (thereby improving stability ofthe hydrazine vapor output); and (4) the hydrazine/adsorbent has a largesurface area for the vaporizing anhydrous hydrazine, as compared toliquid hydrazine, resulting in stable, high hydrazine vapor output. U.S.Pat. Nos. 9,610,550 and 9,410,191, incorporated herein by reference,describe methods of delivering clean and dry gas from multiplecomponents solution.

Referring now to the drawings, wherein the showings are for the purposeof illustrating embodiments and presenting experimental values of thepresent invention only and not for purposes of limiting the same, FIG. 1shows a perspective cross-sectional view of an exemplary storage device100 with a substrate 102 disposed therein in accordance with one or moreembodiments of the present disclosure.

As shown in FIG. 1 , storage device 100 can include a housing 101 with ahead space 103 defined therein. Substrate 102 (also referred to hereinas a “wick material” and “wick reservoir”) may be disposed withinhousing 101 of storage device 100. In various embodiments, the vaporphase of a process solution (e.g. hydrazine solution or hydrogenperoxide solution) provided within the housing will be produced in thehead space 103 of storage device 100 such that the vapor phase may thenbe adsorbed onto the surface of the substrate 102 to dilute the processsolution within the substrate. The housing 101 may be configured toallow a carrier gas (e.g., a dry carrier gas) to flow through the headspace 103, or to allow a vacuum to be drawn through the head space 103,for example, through inlet port 104 a and outlet port 104 b of housing101 to produce a gas stream containing the gas phase substantially alongaxis A. In various embodiments, head space 103 contained within housing101 may be separated from the process solution (e.g., hydrazine solutionor hydrogen peroxide solution) by substrate 102. While an exemplaryhousing 101 is shown as a tubular housing that has opposing inlet/outletports 104 a/104 b, it should be understood that housing 101 may beformed in any shape suitable for storage and/or delivery of the gasstream to a critical process, application, or other storage vessel.

In various embodiments of the present disclosure, the substrate may bespiral-wound (e.g., a continuous, helical form with one or more layers,as shown in FIG. 2 ). In other embodiments, the substrate may be cutinto individual layers, which may be arranged as substantiallyconcentric cylinders within the housing. As shown in FIG. 2 , substrate102 may have one or more layers (e.g., layers 105, 107, and 109). Layers(105, 107, 109) may be disposed in housing 101 as a spiral or may bedisposed in substantially cylindrical layers about axis A of housing101. In various embodiments, substrate 102 may be formed as a mesh, awoven fabric, or a non-woven fabric, and may have been treated with amechanical finishing process, such as spun bonding, needle bonding,perforation bonding, carding, or any combination thereof. In variousembodiments, the substrate may be surface treated to make the surfacehydrophilic and/or enhance the capillary effect. In various embodiments,the surface treatment includes, but is not limited to, exposure toozone, plasma, oxygen treatments and/or other chemical modificationtreatments.

In other embodiments, the morphology of the substrate (e.g., adsorbentor absorbent porous material) can be monolithic or divided forms, suchas one or more bricks, one or more blocks, a powder, one or more beads,one or more particles, one or more pellets, one or more extrudates,etc., and may be formed from a porous absorbent/adsorbent materialhaving a large surface area for increased absorption/adsorption of theprocess solution to thereby dilute the process solution within thesubstrate. In various embodiments, the substrate is a porous structurewith a surface area ranging from about 100 m²/g to about 1000 m²/g, suchthat the substrate is configured to adsorb over 30% w/w hydrogenperoxide, such as over 50% w/w hydrogen peroxide, over 100% w/w hydrogenperoxide, over 200% w/w hydrogen peroxide, over 800% w/w hydrogenperoxide, 1000% w/w hydrogen peroxide, or 1900% w/w hydrogen peroxide.

Exemplary substrates include, but are not limited to, activated carbonand porous metal oxides such as aluminum oxide, titanium dioxide,silica, zirconium oxide, and zeolite. Additional substrates may include,but are not limited to, polyolefins such as polyethylene (PE),polypropylene (PP), and polymethylpentene (PMP). Additional substratesmay include, but are not limited to, polyesters such as polyethyleneterephthalate (PET) and polybutylene terephthalate (PBT),polyethylene/polyethylene terephthalate co-polymer (PE/PET),polyethylene/polypropylene co-polymers, Hydrophilic High DensityPolyethylene (HDPE), Hydrophobic High Density Polyethylene (HDPE),Hydrophilic UHMW Polyethylene, and Hydrophobic UHMW Polyethlyene.Additional exemplary substrates may include, but are not limited to,polycarbonate and polysulfone fluoropolymers such aspolytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), andpolyvinylidene fluoride (PVF). Additional exemplary substrates mayinclude, but are not limited to, natural polymeric materials such asrayon, silk, tencel, and sponge materials. Additional exemplarysubstrates may include, but are not limited to, alumina, silicondioxide, quartz, carbon molecular sieve, carbon pyrolyzate, high silicazeolite, polypyridine, polyacrylates, polyacrylic acid, polyacrylicacid/acrylate co-polymers, polyacrylamides, polyacrylate/acrylamideco-polymers, cellulosic materials, etc. In various embodiments, thesubstrate 102 is formed as a non-woven fabric, such as a PTFE fabric.

In other embodiments, substrate 102 may be a hydrogel configured toabsorb/adsorb the process solution thereon, as shown in FIG. 3 . As usedherein, the term “hydrogel” is used broadly to refer to a macromolecularpolymer gel constructed of a three-dimensional (3D) network ofhydrophilic polymeric materials that can absorb a large amount water orother aqueous solutions. Most of the hydrogel materials have across-linked structure so they can maintain their 3D network, even whenthey are dry. Without being bound by theory, hydrogels are typicallysynthesized from hydrophilic monomers by either chain or step growth,along with a functional crosslinker to promote network formation.Exemplary hydrogels useful as a substrate 102 of the storage device 100provided herein include, but are not limited to, polyethylene glycol(PEG), polyvinyl alcohol (PVA), polyvinylpyrrolidone (PVP),polypyridine, or any combination thereof. In one or more embodiments,substrate 102 may be a 20% or 40% PEG hydrogel. For example, PEGhydrogel is an inert, highly hydrophilic, absorbent material that canretain anhydrous hydrogen peroxide and give an output of anhydroushydrogen peroxide vapor of more than 1500 ppm in a 500 sccm nitrogenflow at 35° C. Significantly, no decomposition was observed whentreating PEG hydrogel with anhydrous hydrogen peroxide for 24 hours.

Using such polymeric materials as a reservoir of a process gas minimizesthe possibility of having entrained liquid droplets in the gas streambeing delivered. As such, dry PEG hydrogel is suitable for use as asubstrate based on compatibility, absorbance and retention with variousprocess solutions. PEG has hydrophilic chains and can combine with waterand, e.g., hydrogen peroxide with hydrogen bonds. As such, without beingbound by theory, the retention rate of, e.g., hydrogen peroxide, isdependent on the density of the PEG chains in its 3D network (i.e., theratio of the mass and the volume of the dry gel) which is tailorable byadjusting the concentration of PEG molecules in water before drying.Thus, the ratio of the mass and the volume of dry gel may be varieddepending on the content of the anhydrous hydrogen peroxide to bestored/delivered by the storage device.

In various embodiments, the hydrogel substrate 102 may be wrapped in awoven or non-woven mesh, such as a PTFE mesh. In various embodiments,the substrate may be surface treated to make the surface hydrophilicand/or enhance the capillary effect. In various embodiments, the surfacetreatment includes, but is not limited to, exposure to ozone, plasma,oxygen treatments and/or other chemical modification treatments.

In various embodiments, one or more separators (e.g., separators 106,108) may be disposed adjacent to substrate 102 within the housing 101.For example, each separator (106, 108) may be disposed between eachlayer (105, 107, 109) of substrate 102 (e.g., a spiral-wound mesh) suchthat separator (106, 108) supports and separates layers (105, 107, 109)of substrate 102. As such, separator (106, 108) may be spiral-wound, maybe formed from individual, concentric cylindrical layers, or may beformed in any other shapes/sizes as necessary to support and/or separatethe individual layers of the substrate 102. The separator (106, 108) maybe formed from any of the materials from which the substrate 102 may beformed. In various embodiments, the separator (106, 108) is formed fromthe same material as the substrate 102 or from a different material fromthe substrate 102. In various embodiments, the separator (106, 108) maybe formed from PTFE.

Turning now to FIG. 2 , there is shown a perspective view of a portionof substrate 102 wound in a spiral about axis A. Though not shown inFIG. 2 , substrate 102 may further include separator (106, 108;designated by the dot-dashed line 202) rolled into the spiral with thesubstrate 102, such that each layer of substrate 102 (105, 107, 109), isseparated by the rolled separator 202.

FIGS. 4A-4E show an exemplary embodiment of storage device 100 inaccordance with one or more embodiments of the disclosure. FIGS. 4C and4D illustrate a side cross-sectional view and a top cross-sectional view(taken along line D-D of FIG. 4C), respectively. As shown, substrate 102(i.e., wick material) was rolled into a spiral form (as shown in FIG. 2) and inserted into housing 101. Housing 101 is therefore configured toallow a carrier gas (e.g., nitrogen) to flow through a head space 103 ofthe substrate 102 to traverse the housing 101 via input port 104 a andoutput port 104 b. As shown in FIGS. 4D and 4E, caps 160 may be used toclose off input port 104 a and output port 104 b. Substrate 302 maycontain the adsorbed process solution 170 and the flow of the carriergas 180 (indicated by directional arrow) may allow for relativelyparallel flow of vapor from the process solution through head space 103and output port 104 b to an application process.

In various embodiments, the process solution provided in the storagedevice may be a liquid or gaseous solution. For example, the processsolution may be hydrogen peroxide (e.g., an aqueous hydrogen peroxidesolution or an anhydrous hydrogen peroxide solution), hydrazine (e.g.,an aqueous hydrazine solution, an anhydrous hydrazine, or any anhydrousderivative of hydrazine, such as, for example, mono-methyl hydrazine,tertiary butyl hydrazine, methylhydrazine, dimethylhydrazine, etc.), andany derivative thereof.

Thus, the substrate may be used for storing, e.g., anhydrous hydrazineand dispensing hydrazine vapor to a critical process, application orstorage vessel. As described above, liquid or gaseous anhydroushydrazine may be absorbed into the porous materials by physicalabsorption. The quantity and/or concentration of the anhydrous hydrazineloaded into the storage device can therefore be controlled by varyingthe contact time with the substrate or by varying the type and porosityof the materials used to form the substrate. In various embodiments, thestorage device is configured to store about 30 to 1900 weight percent,for example about 30 to 800 weight percent of the processsolution/substrate complex, or about 30 to 100 weight percent of theprocess solution/substrate complex. Thus, in various embodiments, thestorage device is configured to store about 100 weight percent, about200 weight percent, about 300 weight percent, about 400 weight percent,about 500 weight percent, about 600 weight percent, about 700 weightpercent, about 800 weight percent, about 900 weight percent, about 1000weight percent, about 1100 weight percent, about 1200 weight percent,about 1300 weight percent, about 1400 weight percent, about 1500 weightpercent, about 1600 weight percent, about 1700 weight percent, about1800 weight percent, or about 1900 weight percent of the processsolution/substrate complex. When the storage device is in use fordelivering a process gas (e.g., hydrazine vapor), the gas is deliveredby producing a low pressure (i.e., vacuum) downstream of the storagedevice or by flowing an inert carrier gas through the storage device. Invarious embodiments, output of the hydrazine vapor can be controlled byvarying one or more of the pressure or the flow rate of the inertcarrier gas.

The following examples are intended to illustrate, but not limit, theinvention.

Example 1 PTFE Wick for Anhydrous Hydrogen Peroxide

The purpose of this example is to determine the compatibility andabsorbency of hydrophilic PTFE with anhydrous hydrogen peroxide.Hydrophilic PTFE PWP-100-100 samples do not react with 30 wt %, 45 wt %and anhydrous peroxide. The material has been shown to absorb hydrogenperoxide at least four times its own mass. Test results are summarizedin Table 1.

TABLE 1 Sample Comparison of 30, 70, & >90 wt. % Peroxide Absorption andRetention by Hydrophilic PTFE Materials over 24 hours. Dry material H₂O₂wt. weight absorbed % wt loss % wt. Sample Material wt % H₂O₂ (g) (g)uptake (g) Retention Reaction Shape 1 PTFE 30 0.124 0.515 415 0 100 NRRod 2 PTFE 45 0.126 0.693 550 0.03 95.7 NR Rod 3 PTFE anhydrous 0.1570.757 482 0 100 NR Rod

Thereafter, the output of anhydrous hydrogen peroxide vapor was testedfor hydrophilic PTFE samples, PTFE WPW-100-100 and PTFE WPW-0450-80,respectively, over time at 35° C./500 sccm nitrogen, where the averageoutput was calculated between 20 and 100 minutes. The parameters forthis experiment are shown in Table 2. The PTFE sheets were folded into4-layered strips and rolled into cylinders with hydrophobic PTFE mesh.

TABLE 2 Test Parameters for PTFE Material Wick Carrier Basic Basic MassWick Size Process Gas Sample Weight Weight Required Required Temp FlowPressure # Polymer (g/m2) (g/in²) (g) (In²) (° C.) (sccm) (torr) WPW-Hydrophilic 30 0.019 2.33 122.63 35 500 760 100-100 PTFE WPW-Hydrophilic 34 0.022 2.33 105.91 35 500 760 045-80 PTFE

While the WPW-0450-80 sample had a higher maximum vapor output than theWPW-100-100 sample, its output decreased after reaching this peak andnever stabilized. Table 3 provides a summary of the anhydrous hydrogenperoxide vapor output for the PTFE samples tested.

TABLE 3 Anhydrous Peroxide Vapor Output Summary for PTFE Material AveFlow Rate Avg H₂O₂ Maximum Avg Run for Total Run Ave Oven Flow Rate H₂O₂Conc H₂O₂ Conc Time Time Temperature by 465 L by 465 L by 465 L Sample(min.) (mg/min) (° C.) (mg/min) (PPM) (PPM) WPW-100- 961 1.05 35 1.492026 1957 100 WPW-045- 1267 0.80 35 Not Stable 2326 Not Stable 80

Example 2 Micro-Porosity, Non-Woven Fabric for Anhydrous Peroxide VaporOutput

This example provides test information for use of a micro-porous,synthetic, non-woven, wicking fabric as the substrate of the storagedevice for use with anhydrous hydrogen peroxide, along with adetermination of whether the cartridge had comparable outputconcentration to the BRUTE® peroxide vaporizer (BPV), solvent-based,BRUTE® Peroxide 120E (BP) under similar temperature and carrier gas flowconditions. The wick vaporizer (storage device) was initially validatedwith 50% w/w hydrogen peroxide before testing with anhydrous HP due tosafety concerns.

The test storage device (anhydrous hydrogen peroxide vaporizer (APV)cartridge) used a spiral-wound, hollow-core, hydrophilic, non-wovenpolymer, wick reservoir element (substrate) with an integral mesh PTFElayer separator. The experiment also tested incorporation of an internalorifice to increase upstream gas retention time in the wick's core, anda wick material that functions as a solid, diluting mass for a specificquantity of anhydrous hydrogen peroxide.

The hydrogen peroxide (HP) vapor output test was performed with variouswick materials and the spiral-wound wick core was sized to fit inside a250 mL BPV. The Brute Peroxide Test/Fill Station was used to determinevapor pressure from the H₂O₂ loaded on the substrate/wick. Theconstructed APV test cartridge was used to check output concentrationresponse of the test, at various conditions, using a 30% w/w hydrogenperoxide liquid loading of anhydrous hydrogen peroxide solution onto thesubstrate/wick material. Equation (1.1) was used for the loadingrequirement:AP (g)/(Wick (g)+AP(g))×100%=30% w/w of anhydrous hydrogenperoxide  (1.1)

This test used a pre-determined 1 gram quantity of anhydrous hydrogenperoxide using various Polyethylene/Polyethylene terephthalate (PE/PET)materials. In order for a wick/substrate material to be eligible forthis test, it must have a minimum adsorbancy of 42.9% to ensure that thewick material will adsorb enough liquid to make a 30% w/w H₂O₂ system.Here, the liquid added is 1 g of anhydrous H₂O₂ (assumed to be 100% w/wH₂O₂). In order to create a 30% w/w H₂O₂ system, the wick must weigh2.33 g, which was calculated as follows:% Adsorbancy,min=100%*(Liquid adsorbed mass/fabric mass)=100%*(1 g/(2.33g))=42.9%

In addition, the wick must be able to retain the loaded liquid withoutdripping. Assuming that retention scales linearly with liquid adsorbed,the following relation determines the minimum retention:% Retention,min=100%*(Liquid added/Liquid capacity)Liquid capacity=% Adsorbancy,measured*fabric mass/100%Assuming % Absorbancy,measured is 250% (for example) and using 2.33 g ofwick materialLiquid capacity=250%*1.33 g/100%=3.33 g% Rentention,min=100%*(1 g/3.33 g)=30%, where 1 g of liquid loading isfrom anhyrous peroxide

Seven non-woven polymers were selected and considered suitable for theexperiment based on prior absorbance and retention tests, which aresummarized in the abbreviated Table 4. Such results were based on twosquare inch samples of sheet, non-woven wicking fabric.

TABLE 4 30, 70% w/w HP and anhydrous HP Absorption and Retention byNon-Woven Material over 24 Hours. Data was omitted where absorption wasnot quantified and for materials that were not used for the wick outputtesting. Liquid Loss H₂O₂ Dry Over Concentration Fabric Liquid 24 TestedMass Absorbed % Hours % Sample # Polymer (% w/w) (g) (g) Absorbed (g)Retained Reaction Shape Description 5 PE/PET 30 0.03 0.44 1467 0.09 79.5NR Sheet Card/Calendared 8 PP/40 30 0.06 0.07 117 0.03 57.1 NR SheetSpunbound 9 PP/70 30 0.10 0.80 800 0.1 87.5 NR Sheet Meltblown 11aPET/RAY 30 0.07 0.96 1371 0.17 82.3 NR Sheet Hydroentangled 5 PE/PET 700.05 0.55 1100 0.04 92.7 NR Sheet Card/Calendared 8 PP/40 70 0.05 0.611220 0.11 82.0 NR Sheet Spunbound 9 PP/70 70 0.08 0.87 1088 0.10 88.5 NRSheet Meltblown 11a PET/RAY 70 0.07 0.99 1414 0.00 100.0 NR SheetHydroentangled 2 PE/PET 99 1.15 1.15 1917 0.09 92.2 NR Sheet Card/ThruAir 5 PE/PET 99 0.49 0.49 817 0.06 97.8 NR Sheet Card/Calendared 8 PP/4099 0.05 0.44 880 0.02 95.5 NR Sheet Spunbound 9 PP/70 99 0.09 0.82 9110.12 85.4 NR Sheet Meltblown 11a PET/RAY 99 0.06 0.83 1383 0.00 100.0 NRSheet Hydroentangled 12  Lyocel/PET 99 0.13 0.34 262 0.03 91.2 NR SheetSpunlace 11b PP 99 0.10 0.49 490 0 100.0 NR Sheet Needle

It was determined that depending on the total mass of the wickingfabric, the net weight of HP mass can be dramatically affected. Theheavier the wick, the more HP mass can be accommodated per cartridgevolume and still maintain the 30% w/w. The separator/support materialweight was not included in calculating the 30% w/w for the belowdescribed experiment, only the substrate/wick and the solution weights.The benefit of the wicking fabric is to safely constrain a practicalamount of anhydrous HP in a solid structure during handling. The wickeliminates the separation problem that can occur in liquid solvents and,depending on the exact definition of concentration, provides higherdeliverable volumes of concentrated hydrogen peroxide vapor.

As shown in FIG. 5 , a manifold 1000 was constructed for the pre-drydown of the wick material before filling with anhydrous hydrogenperoxide for the flow test experiment. Purified nitrogen 1005 wassupplied to a 500 sccm air rotameter (i.e. R-1) at 25 psig using aforward pressure regulator (i.e. PR-1). R-1 was set to 500 sccm to flowto an assembled APV (storage device 100), which includes a substrate1020 (i.e. a wick material with separator). The APV was place in a B-M-Aenvironmental chamber 1010 and the chamber 1010 was set to 45° C. Theoutlet of APV was sent to a relative humidity (RH) probe to quantify themoisture content in the wick material. APV remained in the heatedenvironmental chamber 1010 with 500 sccm of nitrogen flow until themoisture at an RH probe 1025 was below 5% RH. After the wick wassufficiently dried, two PTFE three-way valves (i.e. V-1 and V-2) wereused to isolate APV for transport to a glove box for filling withanhydrous hydrogen peroxide.

As shown in FIG. 6 , a manifold 1100 was utilized for the vapor flowtest/experiment in this Example. Purified nitrogen 1105 was supplied toMFC-1 and MFC-2 at 25 psig using a forward pressure regulator (PR-1). A5 SLM Brooks MFC (MFC-1) (Brooks SLA5850 S-Series Mass Flow Controller)controlled the flow rate of carrier gas 1105 to (storage device 100),which includes a substrate 102 and separator strips (106, 108; FIGS. 1and 2 ) and a 7/64″ diameter orifice reducer (not shown). A ⅓ PSI checkvalve (CV-1) was installed downstream of the MFC to prevent chemicalexposure. A 0-30 PSIG pressure transducer (PT-1) was used to monitor thepressure upstream of test vaporizer 1015. The APV cartridge was filledwith 1 gram of anhydrous HP to add H₂O₂ vapor to the carrier gas. UsingEquation (1.1), the total mass of the wick sample was 2.33 g. The APVwas placed inside the environmental chamber 1110 (B-M-A Inc.Environmental Chamber (Model TC-4)) and its temperature was keptconstant during each test. The dilution and carrier gas temperatureswere controlled to the same temperature as environmental chamber 1110using TC-1 and TC-3. PTFE valves (V-1 and V-2) were used to direct gasflow directly to analyzer 1120 (zero gas) or through APV 1015. A PSIcheck valve (CV-2) was installed downstream of MFC-2 prevented chemicalexposure. The analyzer 1120 was used to measure the H₂O₂ vapor outputduring the test. A PLC (Programmable Logic Controller) was used torecord the Ozone analyzer reading and pressure reading from PT-1. TheH₂O₂ scrubbers decompose H₂O₂ from the process gas into O₂ and H₂O. Thegas lines between the APV outlet and scrubber were heat traced and keptheated on the skin such that the inline outlet gas temperature (TC-2)stayed above the environmental chamber temperature. The setup, excludingenvironmental chamber 1110, was placed inside a fume hood.

The environmental chamber temperature and inlet gas temperature were setto a temperature listed in Table 5. Initially, the valves werepositioned to allow the gas to flow to the analyzer. For thisexperiment, the carrier gas flow rate was 500 sccm, which corresponds tothe max flow of the BPV. The APV output was diluted with 500 sccm of N₂.The dilution gas line temperature was set to a temperature listed inTable 5. Once the temperatures were stabilized under these conditions,analyzer 1120 was zeroed. Once a stable zero reading was obtained, datacollection from analyzer 1120 began. The vessel of APV 1015 was placedin environmental chamber 1110 for 30 minutes before the test commencedto allow the vessel to come to temperature. After 30 minutes, the valveswere positioned to allow the gas the flow through APV 1015 and toanalyzer 1120. After output reached a maximum and began to fall, thevalves were positioned to allow the gas to flow directly to analyzer1120 and to isolate APV 1015. This data was used to determine a zerodrift. After 15 minutes, data collection was discontinued. Thetemperature controllers were shut down and the lines and analyzer 1120were allowed to return to room temperature before the gas flow wasdiscontinued.

TABLE 5 Test parameters Wick Wick Basis Bsis Mass Size Process WeightWeight Required Required Temp Test Sample # Polymer Process (g/m2)(g/in2) (g) (in2) (° C.) 1 5 PE/PET Card/Calendared 40 0.026 2.33 90.4235 2 9 PP/70 Melt Blown 70 0.045 2.33 51.67 35 3 11a PET/RAYHydroentangled 55 0.035 2.33 65.76 35 4 12  Lyocel/PET Spunlace 1000.065 2.33 36.17 35 5 2 PE/PET Card/Thru Air 40 0.026 2.33 90.42 35 611b PP Needle 71 0.046 2.33 50.94 35 7 8 PP/40 Spunbound 40 0.026 2.3390.42 35

The structure of the test wicks in the APV cartridge of Example 3 didincorporate the hollow-core design shown in FIG. 2 , where the APVincluded a spiral-wound and had a hollow core substrate. Morespecifically, the APV was a spiral-wound, hollow-core, 4-layer,non-woven, hydrophilic wick element without mesh separators. Thenon-woven wick material and Teflon separator were rolled into a hollowcylindrical packing and fitted loosely into the APV cartridge tube, asshown in FIGS. 4A-4E.

Table 6 summarizes the results obtained. Using Antoine's equation, thetheoretical vapor concentrations from a 100 wt % hydrogen peroxidesolution at 35° C. is 5063 ppm for hydrogen peroxide. As with the 50PVtests, the procedure was deviated from to extend the runs to near zeroppm output rather than stopping 30 minutes after reaching peak value.This run extension required the system to be operated over 2 days in 5of the 7 tests. Each graph shown in FIGS. 7-18 is a result for the runoutput on that day, starting from zero minutes, whether it was a singlerun or a continuation. However, due to the larger, bulky size of the APVcartridges with their isolation valve block, it was not possible tomeasure the minute interim mass losses. As a result, Table 6 shows somemissing average flow rate data, marked as “nt” for not taken.

The common observation of all the individual runs was that there was afaster rise to peak hydrogen peroxide vapor concentration in comparisonto the 50% solution. However, AP peak concentration values did not riseappreciably.

The top three non-woven wicks for peak anhydrous peroxide concentrationwere: Sample 11 (3243 ppm), Sample 8 (3171 ppm), and Sample 5 (2978ppm). Compared to the 50PV tests, the second day APV peak output runvalues were much closer (6 to 12%) to the first day run. Sample 12 wasthe exception: the 2nd day run peak value was 35% higher than the firstday. Coincidently, the rayon based Sample 12 took twice the amount oftime to dry.

With respect to longevity of output, the top three materials were:Sample 5 (2750 ppm), Sample 11 (2213 ppm), and Sample 9 (2134 ppm) onaverage. There was no color change or any measurable exotherm,indicating rapid oxidation.

Table 7 shows the summary of results of the vapor pressure rise tests.Sample 9 was not tested due to anhydrous H₂O₂ leaking out of the wickroll during filling. Sample 12 was not tested due to scarring of thefabric during anhydrous H₂O₂ flow testing. Sample 5 had the largestaverage pressure rise over 60 minutes. However, those pressure risetests were done at a higher average temperature than all other pressurerise tests. As shown in FIG. 19 , Sample 8 showed a strong correlationbetween average temperature and vapor pressure after 60 minutes. Thistrend is consistent and supported by Raoult's law. However, Raoult's lawpredicts a vapor pressure of 5.3 torr from a 90% w/w H₂O₂ in watersolution at 31.83° C. After 60 minutes, every material filled withanhydrous peroxide had a vapor pressure above this value. Additionally,the vapor pressure was still increasing at 60 minutes for every materialtested.

TABLE 6 Anhydrous Peroxide Vapor Output Summary Avg Flow Maximum Ratefor Avg H2O2 H2O2 Avg H2O2 Total Run Avg Oven Flow Rate Conc by Conc RunTime Time Temperature by 465 L 465 L by 465 L Run Test (min) (mg/min) (°C.) (mg/min) (PPM) (PPM) Sequence 1a 222 nt 36 2.11 2978 2770 1 of 2 1b339 2.35 35 1.21 2835 1590 2 of 2 2a 223 nt 35 1.78 2602 2346 1 of 2 2b1520 0.63 35 1.40 2773 1846 2 of 2 3a 495 nt 35 0.92 1993 1213 1 of 2 3b453 1.03 37 0.90 1305 1184 2 of 2 4a 228 nt 35 0.84 1218 111 1 of 2 4b5689 0.12 35 0.70 1856 920 2 of 2 5a 391 nt 35 1.15 1829 1507 1 of 2 5b441 1.15 36 1.09 2085 1434 2 of 2 6  380 1.1  35 1.91 3243 2513 1 of 17  373 2.14 35 2.05 3171 2698 1 of 1

TABLE 7 Vapor Pressure Rise Test Result Summary Avg Avg Pressure AveragePressure Rise in 60 Pressure Stability for Sample Temperature After 60min 10 minutes? Test # Polymer Process (° C.) min (torr) (torr/min)(Notes) 1 5 PE/PET Card/Calendared 31.83 19.57 0.30 x 2 9 PP/70 MeltBlown — — — (Fill failed) 3 11a PET/RAY Hydroentangled 22.4  9.91 0.13 x4 12  Lyocel/PET Spunlace — — — (Scarred during flow test) 5 2 PE/PETCard/Thru Air 29.85 18.18 0.28 x 6 11b PP Needle 21.73  9.07 0.12 x 7 8PP/40 Spunbound 21.93  8.67 0.12 x

All the non-woven samples transmitted hydrogen peroxide vapor. Agenerally inverse relationship of liquid peroxide percent absorbency topeak peroxide vapor dispersion concentration emerged with the APV flowtests. With the exception of Sample 12, Table 8 shows consistently thatthe non-woven fabrics in this test group, with the lowest percentabsorbency of AP had, correspondingly, the greatest peak vapordispersion concentration measured in ppm.

The average vapor output concentration in ppm also follows a similarinverse relationship to percent absorbency, again with the exception ofSample 12. Polar, hydrophilic, rayon-based fabrics, Sample 11 and Sample12 provide the lowest peak vapor concentration values and werephysically deteriorated in the presence of APV.

TABLE 8 A Comparison of Maximum and Average Vapor [C] to percentAbsorbency Maximum Avg H2O2 H2O2 Dry Liquid Conc by Conc by BondingSample [C] Wt. Fabric added % 465 L 465 L Process # Polymer % H2O2 Wt.(g) (g) Absorbed (PPM) (PPM) Description 2 PE/PET 99 0.06 1.15 1917 20851507 Card/Thru Air 11a PET/RAY 99 0.06 0.83 1383 1993 1213Hydroentangled 9 PP/70 99 0.09 0.82 911 2773 2346 Meltblown 8 PP/40 990.05 0.44 880 3171 2698 Spunbound 5 PE/PET 99 0.06 0.49 817 2978 2770Card/Calendared 11b PP/71 99 0.10 0.49 490 3243 2513 Needle 12 Lyocel/PET 99 0.13 0.34 262 1856 920 Spunlace

Hydrophobic polymers PP or PE/PET produced the greatest peak andlongevity concentration values apparently due to the non-polar,adsorbent polymer structure. To increase hydrophilicity, PP and PET maybe physically altered, increasing fiber cross-sectional area, decreasefiber diameter or increase fiber orientation in the direction oftransport. Molecularly hydrophobic PP and PET fabrics can bemechanically finished in a variety of textile processes to become anadsorbent.

Physical methods to increase surface area per square inch of adsorbentpolymers does not increase the polarity of the molecule. Increasedsurface area allows for weak physical adsorption by Van der Waalinteraction (VdW) between liquid peroxide and the solid polymer. Theexact nature of VdW interactions between AP and non-polar, hydrophobiclong chain polymers is beyond the scope of this report. The measurabledifferences of AP vapor dispersion in a specific test environment may beattributed to the presence of polar and non-polar adsorbent fabricpolymers serving as a liquid storage matrix.

With regard to the different surface finishing processes of thenon-woven materials, the needle-punched fabric of Sample 11 appeared tooffer an advantage of higher 3D surface area per square inch thancarded, melt-blown or calendared pressed. Sample 2 and Sample 5demonstrated the highest measured vapor pressure due to the correlationbetween temperature and vapor pressure at 60 minutes.

Example 3 Micro-Porosity, Non-Woven Fabric For 50 wt. % HydrogenPeroxide Vapor Output

The purpose of this example is to present information regarding amicro-porous, synthetic, non-woven, wicking fabric, 50 wt % hydrogenperoxide vaporizer, 50PV cartridge and determine whether the cartridgehas comparable vapor output concentration to the Brute® peroxidevaporizer (BPV), solvent-based, 3 wt % water content, BRUTE® Peroxidesolution (BP) under similar temperature and carrier gas flow conditions.

This experiment was run using similar methods and test samples to thoseused in Example 2. For this experiment, for a wick material to beeligible for this test it must have a minimum absorbancy of 150% toensure that the wick material will absorb enough liquid to make a 30 wt% H₂O₂ system. Here the liquid added is 2 g of 50 wt % H₂O₂. In order tocreate a 30 wt % H₂O₂ system, the wick must weigh 1.33 g:Absorbancy,min=100%*(Liquid absorbed mass/fabric mass)=100%*(2 g/(1.33g))=150%

The environmental chamber temperature and inlet gas temperature were setto a temperature listed in Table 8. After the peroxide vapor output testhad been performed with each wick material, the spiral-wound wick corewas sized to fit inside a 250 mL BPV. The BRUTE Peroxide Test apparatus(FIG. 6 ) was used to determine vapor pressure rise rate from theH₂O₂/water loaded on the wick. An average measured BP output of 3400 ppmbased on a 25 wt % BP concentration at 35° C. with 500 sccm N₂ carrierflow may be expected. Equation (1.2) represents the loading requirement:HP(g)/(Wick (g)+HP(g)+Water(g))×100%=30 wt % of hydrogen peroxide  (1.2)

The results of the seven non-woven fabrics used were based on two squareinch samples of the respective sheets. Only PET/Rayon and Lyocel/PETnon-woven fabrics are molecularly hydrophilic absorbents characterizedby the ability to uniformly distribute and retain a liquid volumethrough its whole, solid interior, potentially changing its physicalproperties due, in part, to hydrogen bonding. Table 9 summarizes theresults obtained. Test Run 7, Sample 8, was not performed since theliquid did not fully hold on to the wick material during loading.

Using Raoult's Law, the theoretical vapor concentrations from the 50 wt% hydrogen peroxide solution at 35° C. were 1100 ppm for hydrogenperoxide and 31000 ppm for water. Therefore, the water concentration was29 times greater than the hydrogen peroxide vapor under such conditions.Given that the water had a higher vapor pressure under the testconditions, the hydrogen peroxide vapor concentration increased as thehydrogen peroxide solution concentration increased on the wick materialdue to the evaporation of the water content. This partially explains theshape of the wick vapor output curves in FIG. 20 . The initial vaporoutput from four of the six tests are near this theoreticalconcentration.

The theoretical hydrogen peroxide vapor concentration from a 50%hydrogen peroxide solution at 35° C. is represented in FIG. 20 . Sample11a produced the highest peroxide vapor concentration, followed bySample 11b. Sample 2 produced the longest output curve. Using Raoult'sLaw, the results from Sample 11b indicate a 3319 ppm hydrogen peroxidevapor output, which is equivalent to an 82 wt % peroxide solutionconcentration. This vapor output is only slightly below the 3400 ppmseen from the Brute Peroxide 120E solution at 35° C. The theoreticalhydrogen peroxide vapor concentration from an 80% hydrogen peroxidesolution at 35° C. is represented in FIG. 20 .

Table 10 summarizes the additional results from three of the testmaterials: Sample 5, Sample 12, and Sample 11b, respectively. The othersamples could not be tested for this example due to lack of material.Using Raoult's law, the theoretical hydrogen peroxide and water vaporpressures for a 50 wt % hydrogen peroxide solution at room temperature(25° C.) are 0.41 torr and 13.03 torr, respectively. Therefore, thetotal vapor pressure would be 13.44 torr. All three materials vaporpressures were near this theoretical value after 60 minutes.

At 35° C., the hydrogen peroxide vapor concentrations from some of thewick materials wetted with 50% hydrogen peroxide solution, Sample 11a(3025 ppm), Sample 2 (3020 ppm), and Sample 11b (3319 ppm), werecomparable to the Brute Peroxide vapor concentration output (3400 ppm).

The results indicated that hydrogen peroxide vapor output increased aswater content decreased inside the wick. Therefore, anhydrous hydrogenperoxide may be used on these wick materials to eliminate the effects ofwater on hydrogen peroxide output. Since all of the materials did notprovide the same vapor output characteristics, this indicates thatRaoult's law is not the only factor in determining vapor output for wickmaterials, as disclosed herein. The total vapor pressure for the threematerials that were tested, Sample 5, Sample 12, and Sample 11b, werenear the theoretical vapor pressure of 13.4 torr predicted by Raoult'sLaw.

Example 4 Hydrogel Wick for Anhydrous Hydrogen Peroxide

The purpose of this example is to determine the compatibility andabsorbency of a hydrogel to function as a reservoir for anhydroushydrogen peroxide (HP) storage and shipment. Polyethylene glycol (PEG)hydrogel was synthesized by crosslinking linear PEG diacrylate (Mn:700)into a 3D network with a photo crosslinking method. After contacting theanhydrous HP with the dry synthesized PEG network, a single piece,macro-porous, hydrophilic, polymeric reservoir element was formed. Byincorporating the liquid hydrogen peroxide into the 3D polymericstructure of the hydrogel, it was observed that the HP solution wasstabilized and the upstream gas retention time increased due to thefixed surface area of the hydrogel structure.

In this experiment, PEG hydrogel samples with a PEG content of 20% and40% were used to test compatibility and absorbency. The test procedureis described as follows: (1) a piece of dry PEG hydrogel was dipped intoanhydrous hydrogen peroxide for 30 seconds; (2) the mass of the hydrogelbefore and after dipping was recorded; (3) the HP-soaked hydrogel wassealed in a clear plastic vial for 24 hours; (4) throughout the courseof the test, the material was inspected for any evidence of reaction ordeterioration; and (5) after 24 hours, the hydrogel was weighed again.

No reaction was observed when the dry hydrogel was mixed with anhydroushydrogen peroxide, and no color or morphological change was found after24 hours of sitting in a glove box (i.e., environmental chamber). Suchresults indicate that the hydrogel structure is chemically inert andtherefore suitable for use as a substrate in the storage device providedherein. All tested PEG samples absorbed hydrogen peroxide quickly andwith a high absorbency capacity. After the hydrogel absorbed theperoxide, the hydrogel swelled, but kept its original shape. The testresults are summarized in Table 11.

Thereafter, the anhydrous hydrogen peroxide vapor output from the PEGhydrogel substrate/wick was analyzed. For this experiment, the clearplastic vial was provided with an inlet port and an outlet port, throughwhich nitrogen gas was permitted to flow through the hydrogel cartridgeunder a specified temperature range. Each Hydrogen Peroxide Vaporizer(HPV) cartridge element constructed was based on a pre-determinedquantity of anhydrous HP.

An exemplary test HPV (storage device 100) that includes a PEG hydrogelsubstrate 102 (e.g., 90PV filled PEG gel) wrapped in a PTFE meshseparator 202 was prepared for this test. It was observed that the PTFEmesh separator 202 maintained the shape of hydrogel substrate 102 andkept the hydrogel substrate from cracking and collapsing when thehydrogen peroxide was released from the storage device 100.

TABLE 8 Test Parameters Wick Wick Basis Basis Mass Size Process SampleHydrophobic or Weight Weight Required Required Temp Test # PolymerProcess Hydrophilic (g/m2) (g/in2) (g) (in2) (° C.) 1 5 PE/PETCard/Calendared Hydrophobic 40 0.026 1.33 51.67 35 2 9 PP/70 Melt BlownHydrophobic 70 0.045 1.33 29.52 35 3 11a PET/RAY HydroentangledHydrophilic 55 0.035 1.33 37.58 35 4 12  Lyocel/PET Spunlace Hydrophilic100 0.065 1.33 20.67 35 5 2 PE/PET Card/Thru Air Hydrophobic 40 0.0261.33 51.67 35 6 11b PP Needle Hydrophobic 71 0.046 1.33 29.11 35 7 8PP/40 Spunbound Hydrophobic 40 0.026 1.33 51.67 35

TABLE 9 Hydrogen Peroxide Vapor Output Summary Avg H₂O₂ Flow Rate,Maximum Avg Avg Total Avg Oven by 465 L H₂O₂ Conc, H₂O₂ Conc, Flow RateTemperature Reading by 465 L by 465 L Test Time (min) (mg/min) (° C.)(mg/ml) (PPM) (PPM) Notes 1-1a 184 8.48 35 1.08 2073 1478 1-1b 400 2.3035 1.39 2467 1834 Continuation of Previous 2-1  335 5.22 35 1.47 25071931 3-1a 345 4.70 35 1.17 2360 1532 3-1b 212 1.75 35 1.13 3025 1481Continuation of Previous 4-1a 180 9.22 35 0.56 1355 743 4-1b 300 2.53 351.48 2292 1952 Continuation of Previous 4-1c 360 0.11 35 0.14 1147 184Continuation of Previous 5-1a 276 5.04 35 1.05 2287 1378 5-1b 355 3.0135 1.92 3020 2524 Continuation of Previous 6-1a 340 6.26 35 1.47 30581938 6-1b 300 0.80 35 0.58 3319 761 Continuation of Previous

TABLE 10 Vapor Pressure Rise Test Result Summary Average Test 1 PressureTest 2 Pressure Test 3 Pressure Avg Pressure Pressure Rise in 60 minRise in 60 min Rise in 60 min Rise in 60 min Reading in 60 Test Sample #Polymer Process (torr/min) (torr/min) (torr/min) (torr/min) min 1 5PE/PET Card/Calendared 0.12 0.15 0.14 0.14 10.29 4 12  Lyocel/PETSpunlace 0.20 0.18 0.20 0.19 13.16 6 11b PP Needle 0.24 0.20 0.17 0.2014.18

TABLE 11 Sample Comparison of Hydrogen Peroxide Absorption and Retentionby PEG Hydrogel over 24 hours Dry materials H₂O₂ absorbed % wt wt. loss% wt. Materials weight (g) (g) uptake (g) Retention Reaction 20% PEG gel0.31 2.07 663 0 100 NR 40% PEG gel 0.39 2.34 600 0.1 95.7 NR

TABLE 12 Test Parameters Mass of Mass of Mass of Hydrogel 90 HP Hydrogeland Process Temp Test Sample (g) (g) 90 HP (g) (° C.) 1 20% 2.31 1.033.34 35 PEG pellets 2 40% 2.27 1.03 3.30 35 PEG 3 40% 2.31 1.0 3.31 35PEG pellets

For Test 1, the 20% PEG hydrogel was broken into small pieces. It wasloaded into a Teflon bag so that the morphology of the sample wassimilar to the pellets. For Test 2, the 40% PEG hydrogel was kept in itsoriginal shape and loaded as one solid piece into a Teflon bag. For Test3, the 40% PEG hydrogel was cut into small pellets with a diameter ofabout 3 mm and then loaded into a Teflon bag. In each test run, theenvironmental chamber temperature and inlet gas temperature were eachset to the temperature listed in Table 12. The carrier gas flow rate was500 sccm. The output data was recorded until the hydrogen peroxide levelwas close to zero.

For Tests 1-3, the procedure for the hydrogen peroxide output test wasas follows: (1) The PEG hydrogel was wrapped with Teflon mesh to form acylinder cartridge element to fit the vaporizer; (2) Nitrogen wasallowed to flow through the vaporizer at 40° C. until the material wasdry; (3) The hydrogel was loaded with anhydrous peroxide. The hydrogel'smass was recorded before and after loading; (4) The vaporizer wasinstalled into the test chamber; (5) The test was run under theparameters in Table 12. The hydrogen peroxide output concentration wasrecorded until the measurement was close to zero; and (6) The hydrogelwas removed from the vaporizer and reweighed.

The tests were performed using the exemplary P&ID shown in FIG. 8 . HPV(storage device 100) was filled with HP-loaded hydrogel and placedinside the environmental chamber to maintain a constant temperatureduring each test. Analyzer 1120 was used to measure the HP vapor outputduring each test.

Table 13 summarizes the results of the output tests shown in FIGS. 21,22, and 23 , which correspond to Tests 1, 2, and 3, respectively. Theoutput of hydrogen peroxide in all the samples reached a high levelquickly and decreased slowly. As shown in FIG. 23 , the 20% PEG hydrogelpellets had a maximum HP vapor output of 849 ppm at 35° C., whichoccurred 6.6 hours after the test was started. As shown in FIG. 22 , the40% PEG gel had a maximum HP vapor output of 1582 ppm at 35° C., whichfell below 1300 ppm after about 210 minutes, which was faster than the20% hydrogel and the 40% hydrogel pellets. As shown in FIG. 23 , the 40%PEG pellets sample had a maximum HP vapor output of 897 ppm at 35° C.The average of the output was calculated from the output between 30 and300 minute.

After the tests, the PEG gels were weighed again. It was observed thatapproximately 20% of the hydrogen peroxide was retained in 20% hydrogel,but only 2% was retained in 40% PEG sample.

TABLE 13 Anhydrous Peroxide Vapor Output Summary Avg H₂O₂ Maximum AvgFlow Rate Avg H2O2 H₂O₂ H₂O₂ Mass of Percentage Run Avg Oven for TotalFlow Rate Conc by Conc by H₂O₂ of H₂O₂ Time Temperature Run Time by 465L 465 L 465 L retained retained Test Sample (min) (° C.) (mg/min)(mg/min) (PPM) (PPM) (g) (%) 1 20% PEG 1423 35 0.54 unstable 849unstable 0.24 23.3 pellets 2 40% PEG 1129 35 0.72 1.12 1582 1502 0.02 23 40% PEG 1554 35 0.85 unstable 897 unstalbe 0.02 2 pellets

Example 5 Testing of Wick Materials with Anhydrous Hydrazine

The purpose this example to determine the compatibility of selected wickmaterials with anhydrous liquid hydrazine. Four candidate porousadsorbent wick materials were selected: aluminum oxide, activatedcarbon, hydrophilic PTFE and carbon pyrolyzate.

All sample wick materials were washed and dried. The samples were placedinto 50 mL glass vials and submerged in hydrazine. A J-type thermocouplewas used to measure the temperature changing of the anhydrous hydrazine.Any visible changes to the wick material and/or hydrazine will werenoted during this test.

A test apparatus similar to the one shown in FIG. 6 was used for thehydrazine compatibility tests. Aluminum oxide and activated carbon weretested on day 1, PTFE sheet was tested on day 2, carbon pyrolyzatematerial was tested on day 3. To minimize the exposure of hydrazine inthe glove box, hydrazine in the test vials was decanted into a liquidwaste can together on day 4, and a glass pipette was used to remove therest of hydrazine from the bottom of the vials. Following the tests, thevials with materials were left in the glove box without lids to vaporizethe hydrazine before being placed into a solid waste can.

During the activated carbon testing, the temperature increased about 3°C. in short time and the heat release was not sustained. Bubbles wereobserved, but stopped after about 30 minutes. The sample was inspectedafter 24 hours, 48 hours and 72 hours, no color change of the hydrazinewas observed. After the hydrazine was decanted, there were no observablecolor or structural changes of the activated carbon.

During the aluminum oxide testing, the temperature increased about 2.5°C. in short time and the heat release was not sustained. Bubbles wereobserved, but stopped after about 25 minutes. The sample was inspectedafter 24 hours, 48 hours and 72 hours, and no color change of thehydrazine was observed. After the hydrazine was decanted, there were noobservable color or structural changes of the aluminum oxide.

During the carbon pyrolyzate testing, the temperature increased about2.5° C. after the addition of hydrazine with a steep drop due to theaddition of an additional 15 ml of hydrazine. Bubbles were present, butstopped after 1 hour. After 24 hours, no color change of the hydrazinewas found. After the hydrazine was decanted, there were no observablecolor or structural changes of the carbon pyrolyzate material.

During the PTFE sheet testing, the temperature increased about 0.5° C.after the addition of hydrazine. No bubbles were observed. After 24 and48 hours, no color change of the hydrazine was found. After thehydrazine was decanted, there were no observable color or structuralchanges of the PTFE sheet.

Although the invention has been described with reference to the aboveexamples, it will be understood that modifications and variations areencompassed within the spirit and scope of the invention. Accordingly,the invention is limited only by the following claims.

What is claimed is:
 1. A storage device for a process solution, thestorage device comprising: (a) a housing having a substrate disposedtherein; (b) a process solution contained within the housing and influid contact with the substrate such that the solution is adsorbed ontothe substrate, thereby diluting the solution within the substrate andforming a complex; and (c) a head space contained within the housing andseparated from the process solution by the substrate, wherein theprocess solution is a hydrogen peroxide or a hydrazine, and wherein thehousing is configured to allow a carrier gas to flow through the headspace or is configured to allow a vacuum to be drawn through the headspace to produce a gas stream comprising a gas phase of the processsolution to deliver the gas stream to a critical process, application orstorage vessel.
 2. The storage device of claim 1, wherein the processsolution is a liquid solution or a gaseous solution.
 3. The storagedevice of claim 1, wherein the substrate is formed from a materialselected from the group consisting of polyethylene/polyethyleneterephthalate co-polymer (PE/PET), polyethylene/polypropyleneco-polymer, Hydrophilic High Density Polyethylene (HDPE), HydrophilicUHMW Polyethylene, and any combination thereof.
 4. The storage device ofclaim 2, wherein the process solution is an anhydrous hydrogen peroxidesolution or an anhydrous hydrazine solution.
 5. The storage device ofclaim 4, wherein the anhydrous hydrogen peroxide solution or anhydroushydrazine solution contains less than 2% water.
 6. The storage device ofclaim 5, wherein the anhydrous hydrogen peroxide solution or anhydroushydrazine solution contains less than 0.5% water.
 7. The storage deviceof claim 6, wherein the anhydrous hydrogen peroxide solution oranhydrous hydrazine solution contains less than 0.1% water.
 8. Thestorage device of claim 7, wherein the anhydrous hydrogen peroxidesolution or anhydrous hydrazine solution contains less than 0.01% water.9. The storage device of claim 1, wherein the substrate is a porousstructure with a surface area ranging from about 100 m²/g to 1000 m²/g.10. The storage device of claim 1, wherein the substrate is formed froma material selected from the group consisting of alumina, aluminumoxide, titanium dioxide, silica, silicon dioxide, quartz, activatedcarbon, carbon molecular sieve, carbon pyrolyzate,polytetrafluoroethylene (PTFE), polyester (PE), polyethyleneterephthalate (PET), polypropylene (PP), rayon, zirconium oxide,zeolite, high silica zeolite, polymethylpentene (PMP), polybutyleneterephthalate (PBT), Hydrophobic High Density Polyethylene (HDPE),perfluoroalkoxy alkane (PFA), polyvinylidene fluoride (PVF), silk,tencel, sponge materials, polyethylene glycol (PEG), polyvinyl alcohol(PVA), polyvinylpyrrolidone (PVP), polypyridine, polyacrylates,polyacrylic acid, polyacrylic acid/acrylate co-polymers, polycarbonates,polyacrylamides, polyacrylate/acrylamide co-polymers, cellulosicmaterials, and any combination thereof.
 11. The storage device of claim3, wherein the substrate adsorbs 30% w/w or more hydrogen peroxide. 12.The storage device of claim 11, wherein the substrate adsorbs over 100%w/w hydrogen peroxide.
 13. The storage device of claim 12, wherein thesubstrate adsorbs over 1000% w/w hydrogen peroxide.
 14. The storagedevice of claim 13, wherein the substrate adsorbs over 1900% w/whydrogen peroxide.
 15. The storage device of claim 3, wherein thesubstrate is formed as a fabric, a powder, one or more bricks, one ormore blocks, one or more beads, one or more particles, one or moreextrudates, or one or more pellets.
 16. The storage device of claim 3,wherein the substrate is formed as a mesh.
 17. The storage device ofclaim 16, wherein the mesh is spiral-wound within the housing.
 18. Thestorage device of claim 17, further comprising a separator disposedadjacent to the mesh, wherein the separator is configured to support andseparate layers of the spiral-wound mesh.
 19. The storage device ofclaim 18, wherein the separator is formed from PTFE.
 20. The storagedevice of claim 1, wherein the substrate is a hydrogel selected from thegroup consisting of polyethylene glycol (PEG), polyvinyl alcohol (PVA),polyvinylpyrrolidone (PVP), polypyridine, and any combination thereof.21. The storage device of claim 20, wherein the hydrogel is wrapped in aPTFE mesh.
 22. The storage device of claim 1, wherein the quantity ofthe process solution in the device is about 30 to 1900 weight percent ofthe process solution/substrate complex.
 23. The storage device of claim22, wherein the quantity of the process solution in the device is about30 to 800 weight percent of the process solution/substrate complex. 24.The storage device of claim 23, wherein the quantity of the processsolution in the device is about 30 to 100 weight percent of the processsolution/substrate complex.
 25. The storage device of claim 1, whereinthe hydrazine is selected from the group consisting of mono-methylhydrazine, tertiary butyl hydrazine, and dimethylhydrazine.
 26. Astorage device for a process solution, the storage device comprising:(a) a housing having a substrate disposed therein, wherein the substrateis formed from a material selected from the group consisting ofpolyethylene/polyethylene terephthalate co-polymer (PE/PET),polyethylene/polypropylene co-polymer, Hydrophilic High DensityPolyethylene (HDPE), Hydrophilic UHMW Polyethylene, and any combinationthereof; (b) a process solution of contained within the housing and influid contact with the substrate such that the solution is adsorbed ontothe substrate, thereby diluting the solution within the substrate andforming a complex; and (c) a head space disposed between input andoutput ports of the housing and separated from the process solution bythe substrate, wherein the process solution is selected from the groupconsisting of hydrogen peroxide, hydrazine, mono-methyl hydrazine,tertiary butyl hydrazine, dimethylhydrazine, and any derivative thereof,and wherein the housing is configured to allow a carrier gas to flowthrough the head space or is configured to allow a vacuum to be drawnthrough the head space to produce a gas stream comprising a gas phase ofthe process solution to deliver the gas stream to a critical process,application or storage vessel.